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US7271292B2 - Process for distillatively removing piperazine from an ethylenediamine-piperazine mixture - Google Patents

Process for distillatively removing piperazine from an ethylenediamine-piperazine mixture Download PDF

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US7271292B2
US7271292B2 US11/494,733 US49473306A US7271292B2 US 7271292 B2 US7271292 B2 US 7271292B2 US 49473306 A US49473306 A US 49473306A US 7271292 B2 US7271292 B2 US 7271292B2
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piperazine
ethylenediamine
distillation column
color
column
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US20070037980A1 (en
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Michael Jödecke
Ortmund Lang
Gunther van Cauwenberge
Matthias Frauenkron
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms

Definitions

  • the invention relates to a process for continuously, distillatively removing piperazine from an ethylenediamine-piperazine mixture under pressure at elevated temperature, by discharging the ethylenediamine at the top and the piperazine at the bottom of a distillation column.
  • Piperazine finds use in the preparation of pharmaceuticals for human and veterinary medicine, cosmetics and photographic chemicals.
  • a measure employed for the degree of discoloration is usually the so-called color number.
  • the color number is a characteristic value, determined under fixed conditions, for the color of transparent substances, which is usually determined by visual comparison.
  • a frequently used color number in liquids is the APHA (American Public Health Association) color number (Römpp Chemie Lexikon 1995).
  • Piperazine is obtained in desired purity by known processes, by distillative removal of a product mixture.
  • such high-performance distillation apparatus has become available that the ultimately obtained piperazine fraction already has the desired degree of purity.
  • the distillation includes both the removal (isolation) process step and the purification step in one. From an economic point of view, this constitutes a particularly efficient method even if the piperazine first has to be fractionated repeatedly in one or more columns.
  • Piperazine is usually obtained on the industrial scale as one of the products of value in the preparation of various ethyleneamines.
  • the synthesis is based on the reaction of ethylene dichloride (EDC process) or monoethanolamine (MEOA process) with ammonia.
  • Further coproducts of this reaction are ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and higher linear and cyclic ethyleneamines, and also additionally aminoethylethanolamine (AEEA) in the MEOA process.
  • the MEOA process ensures an increased fraction of cyclic compounds, so that it constitutes the preferred process when a piperazine-containing product mix is desired.
  • the ethyleneamine product mix in industrial production is purified and separated usually by means of a battery of columns in continuous operation. First, the ammonia is drawn off in a pressure column, then the process water formed (or added in the EDC process) is distilled off.
  • GB 1 263 588 describes the purification of the product mix by azeotropic removal of impurities in the distillative removal of water.
  • the discoloring components are generally not detectable as individual compounds and are, for example, below the detection limit in the gas chromatography purity check.
  • these compounds are based on acetaldehyde fractions and their condensed subsequent products.
  • the chromophoric compounds are formed only in the course of time, so that a color number change often occurs only after storage to the effect that the desired specification is no longer attained.
  • the invention uses an ethylenediamine-piperazine mixture which is obtained in a manner known per se.
  • the mixture is separated in a distillation column under pressure and at elevated temperature.
  • Suitable for this purpose is customary distillation apparatus with evaporator and condenser.
  • Preference is given to using a distillation column having generally from 10 to 60, appropriately from 30 to 40 theoretical plates in the form of trays, structured packings or random packings.
  • Useful trays include bubble-cap trays, sieve trays, valve trays, Thorman trays, Streuber trays or dual-flow trays.
  • Preferred structured packings are compact sheetlike structures or fabrics of metal or plastic.
  • Advantageous random packings are rings such as Raschig, Intos or Pall rings, saddles such as barrel or Intalox saddles, and also Top-Pak or braids.
  • the ethylenediamine-piperazine mixture is fed into the distillation column in the region of theoretical plates 5 to 20, in particular 10 to 15.
  • the distillation is carried out in the pressure range from 0.5 to 2 bar, preferably from 0.8 to 1.5 bar, and at a temperature in the bottom of the column of from about 140 to about 170° C.
  • the distillation column Owing to the thermal sensitivity of the ethylenediamine-piperazine mixture, it is appropriate to operate the distillation column with an evaporator which has a low wall temperature and a small liquid capacity. Overall, it has been found to be particularly advantageous to use a folding-film or thin-film evaporator. For gentle evaporation, a temperature difference between the vapor and the product side of ⁇ 30° C., in particular ⁇ 20° C. is recommended.
  • the column bottom and the evaporator bottom are configured such that the residence time of the mixture is less than 60 minutes.
  • the ethylenediamine obtained by distillation is discharged at the top of the column and the piperazine at the bottom of the column.
  • the ethylenediamine is fed as reflux back into the distillation column, this being adjusted such that the reflux ratio is from 0.4 to 0.8.
  • the piperazine is subjected directly to a circulation conveying it through an evaporator unit operated at a temperature of from about 160° C. to about 170° C. and returning it into the distillation column.
  • Suitable evaporator units are falling-film evaporators, thin-film evaporators, short-path evaporators or helical-tube evaporators.
  • the piperazine is discharged continuously in vapor form from a side draw in the lower region of the distillation column.
  • the vaporous piperazine from the side draw can subsequently be condensed with a conventional condenser or with a piperazine quench with external cooler, and be obtained and stored in the form of chips or in another form.
  • the piperazine from the side draw has a high purity (piperazine content >99.9% by weight) and a low color number ( ⁇ 30 APHA). It also features improved color number stability.
  • the piperazine which is drawn off in the bottom of the column likewise has a high purity. Since it is used for the preparation of the aqueous piperazine solution, the higher color number does not present any problem.
  • the improved color stability can be tested in a long-term test.
  • the color quality of a compound is determined generally by measuring the transmission of incident light. To this end, a light beam of defined wavelength is radiated through the melt or a solution of a certain concentration in a cuvette of known path length. The percentage of the light energy transmitted at a given wavelength gives rise to a defined color number. For weakly colored solutions, the APHA color scale is used.
  • the color number is measured in a spectrometer calibrated beforehand to the zero point with the water used in a 50 mm plastic cuvette.
  • the piperazine is weighed into the cuvette in pulverized form, and care has to be taken that no excessive heating occurs as a result of friction.
  • the entire operation also has to be carried out rapidly in a place with efficient air extraction, in order to minimize water ingress owing to the hygroscopicity of the piperazine.
  • the piperazine thus obtained had a purity of at least 99.9% by weight, but had unsatisfactory properties with regard to its color, to its color number stability and to its odor and was therefore not saleable. Color numbers of 24 APHA immediately after the finishing and 65 APHA after 3 months were measured.
  • Example 1 The procedure of Example 1 was repeated except that the piperazine discharged at the bottom of the bubble-cap tray column was subjected to a circulation conveying through a falling-film evaporator operated at a temperature of 165° C. and returning it into the column.
  • the residence time of the piperazine in the circulation system was about 40 min. This allowed the thermal stress on the piperazine in the bottom of the column to be reduced.
  • Vaporous piperazine was then drawn off continuously via a side draw above the 4th tray of the bubble-cap tray column, condensed and finished. The ratio between the bottom draw and the side draw amount was approx. 1:1.
  • Piperazine was obtained with a purity of >99.9% by weight.
  • the color number and the color number stability were distinctly improved in comparison to the experiment according to Example 1. Color numbers of 16 APHA immediately after finishing and 42 APHA after 3 months were measured.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a process for continuously, distillatively removing piperazine from an ethylenediamine-piperazine mixture under pressure at elevated temperature, by discharging the ethylenediamine at the top and the piperazine at the bottom of a distillation column. For the purpose of improving the quality of the piperazine, especially its color and color stability, the piperazine is subjected directly to circulation conveying it through an evaporator unit operated at a temperature of from about 160° C. to about 170° C. and returning it into the distillation column. After a residence time of from about 30 min to about 60 min in the circulation system, the piperazine is discharged in vapor form from a side draw in the lower section of the distillation column.

Description

The invention relates to a process for continuously, distillatively removing piperazine from an ethylenediamine-piperazine mixture under pressure at elevated temperature, by discharging the ethylenediamine at the top and the piperazine at the bottom of a distillation column.
Piperazine finds use in the preparation of pharmaceuticals for human and veterinary medicine, cosmetics and photographic chemicals. An important quality feature of piperazine, in addition to its purity (usually determined by gas chromatography), is the degree of discoloration and the color stability.
A measure employed for the degree of discoloration is usually the so-called color number. The color number is a characteristic value, determined under fixed conditions, for the color of transparent substances, which is usually determined by visual comparison. A frequently used color number in liquids is the APHA (American Public Health Association) color number (Römpp Chemie Lexikon 1995).
Piperazine is obtained in desired purity by known processes, by distillative removal of a product mixture. In this context, such high-performance distillation apparatus has become available that the ultimately obtained piperazine fraction already has the desired degree of purity. Thus, the distillation includes both the removal (isolation) process step and the purification step in one. From an economic point of view, this constitutes a particularly efficient method even if the piperazine first has to be fractionated repeatedly in one or more columns.
Piperazine is usually obtained on the industrial scale as one of the products of value in the preparation of various ethyleneamines. In this preparation, the synthesis is based on the reaction of ethylene dichloride (EDC process) or monoethanolamine (MEOA process) with ammonia. Further coproducts of this reaction are ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and higher linear and cyclic ethyleneamines, and also additionally aminoethylethanolamine (AEEA) in the MEOA process.
Both synthetic routes are based ultimately on the oxidation of ethylene (with chlorine or oxygen) to give EDC and ethylene oxide (EO) respectively, and subsequent one- or two-stage reaction with ammonia. Although the MEOA process thus includes an additional synthesis step, the chlorine oxidant is however expensive and formation of salt is additionally unavoidable.
In comparison to the EDC process, the MEOA process ensures an increased fraction of cyclic compounds, so that it constitutes the preferred process when a piperazine-containing product mix is desired.
Irrespective of the selection of the process, the ethyleneamine product mix in industrial production is purified and separated usually by means of a battery of columns in continuous operation. First, the ammonia is drawn off in a pressure column, then the process water formed (or added in the EDC process) is distilled off.
In this context, GB 1 263 588 describes the purification of the product mix by azeotropic removal of impurities in the distillative removal of water.
In contrast, U.S. Pat. No. 3,105,019 describes the addition of organic solvents as entraining agents for piperazine in the distillation, especially for the removal of a piperzine-TEDA fraction.
Although all of the above-described processes afford piperazine or other ethylamine products or product mixtures with sufficient purity, it is not guaranteed that the products will have sufficient color stability even when the color number determined corresponds to the requirements immediately after isolation.
This is because the discoloring components are generally not detectable as individual compounds and are, for example, below the detection limit in the gas chromatography purity check. Especially in the MEOA process, these compounds are based on acetaldehyde fractions and their condensed subsequent products. In this case, the chromophoric compounds are formed only in the course of time, so that a color number change often occurs only after storage to the effect that the desired specification is no longer attained.
These impurities appear especially in the MEOA process, since the amination of MEOA is based on ethylene units which enable the formation of C2 fragments by dehydration and deamination under the reaction conditions. These fragments, especially acetaldehyde and more highly condensed subsequent products, cause lasting deterioration in the product quality, especially in the color stability. However, it is also the case here that these impurities, owing to their inhomogeneity and low concentration, are generally analytically undetectable in the isolated components after distillation.
It was therefore an object of the invention to provide an improved, efficient and economically viable process for preparing pure piperazine with improved quality with regard to color, color stability and odor.
For the achievement of this object, the measures according to the characterizing part of the patent claim are proposed.
The invention uses an ethylenediamine-piperazine mixture which is obtained in a manner known per se. The mixture is separated in a distillation column under pressure and at elevated temperature. Suitable for this purpose is customary distillation apparatus with evaporator and condenser. Preference is given to using a distillation column having generally from 10 to 60, appropriately from 30 to 40 theoretical plates in the form of trays, structured packings or random packings. Useful trays include bubble-cap trays, sieve trays, valve trays, Thorman trays, Streuber trays or dual-flow trays. Preferred structured packings are compact sheetlike structures or fabrics of metal or plastic. Advantageous random packings are rings such as Raschig, Intos or Pall rings, saddles such as barrel or Intalox saddles, and also Top-Pak or braids.
The ethylenediamine-piperazine mixture is fed into the distillation column in the region of theoretical plates 5 to 20, in particular 10 to 15. The distillation is carried out in the pressure range from 0.5 to 2 bar, preferably from 0.8 to 1.5 bar, and at a temperature in the bottom of the column of from about 140 to about 170° C.
Owing to the thermal sensitivity of the ethylenediamine-piperazine mixture, it is appropriate to operate the distillation column with an evaporator which has a low wall temperature and a small liquid capacity. Overall, it has been found to be particularly advantageous to use a folding-film or thin-film evaporator. For gentle evaporation, a temperature difference between the vapor and the product side of ≦30° C., in particular ≦20° C. is recommended. The column bottom and the evaporator bottom are configured such that the residence time of the mixture is less than 60 minutes.
The ethylenediamine obtained by distillation is discharged at the top of the column and the piperazine at the bottom of the column. The ethylenediamine is fed as reflux back into the distillation column, this being adjusted such that the reflux ratio is from 0.4 to 0.8. According to the invention, the piperazine is subjected directly to a circulation conveying it through an evaporator unit operated at a temperature of from about 160° C. to about 170° C. and returning it into the distillation column. Suitable evaporator units are falling-film evaporators, thin-film evaporators, short-path evaporators or helical-tube evaporators. After a residence time of from 30 min to about 60 min in the circulation system, the piperazine is discharged continuously in vapor form from a side draw in the lower region of the distillation column.
The vaporous piperazine from the side draw can subsequently be condensed with a conventional condenser or with a piperazine quench with external cooler, and be obtained and stored in the form of chips or in another form.
The piperazine from the side draw has a high purity (piperazine content >99.9% by weight) and a low color number (<30 APHA). It also features improved color number stability. The piperazine which is drawn off in the bottom of the column likewise has a high purity. Since it is used for the preparation of the aqueous piperazine solution, the higher color number does not present any problem.
The improved color stability can be tested in a long-term test.
In the color number test, the color quality of a compound is determined generally by measuring the transmission of incident light. To this end, a light beam of defined wavelength is radiated through the melt or a solution of a certain concentration in a cuvette of known path length. The percentage of the light energy transmitted at a given wavelength gives rise to a defined color number. For weakly colored solutions, the APHA color scale is used.
The color number is measured in a spectrometer calibrated beforehand to the zero point with the water used in a 50 mm plastic cuvette. The piperazine is weighed into the cuvette in pulverized form, and care has to be taken that no excessive heating occurs as a result of friction. The entire operation also has to be carried out rapidly in a place with efficient air extraction, in order to minimize water ingress owing to the hygroscopicity of the piperazine.
The invention is illustrated in detail with reference to the examples which follow.
EXAMPLE 1 Comparative Example, Non Inventive
The experiments were carried out with a DN 50 bubble-cap tray column with 70 trays.
1500 g/h of a mixture of approx. 90% by weight of ethylenediamine and approx. 10% by weight piperazine were introduced. The feed was at tray 26. The reflux ratio was about 1:2. The column was operated at an absolute pressure of 1 bar, a top temperature of approx. 117° C. and a bottom temperature of approx. 150° C. The evaporation at the bottom of the column was effected with a circulation evaporator. The ethylenediamine was drawn off at the top of the column with high purity; the piperazine was drawn off at the bottom of the column. The piperazine thus obtained had a purity of at least 99.9% by weight, but had unsatisfactory properties with regard to its color, to its color number stability and to its odor and was therefore not saleable. Color numbers of 24 APHA immediately after the finishing and 65 APHA after 3 months were measured.
EXAMPLE 2 Inventive
The procedure of Example 1 was repeated except that the piperazine discharged at the bottom of the bubble-cap tray column was subjected to a circulation conveying through a falling-film evaporator operated at a temperature of 165° C. and returning it into the column. The residence time of the piperazine in the circulation system was about 40 min. This allowed the thermal stress on the piperazine in the bottom of the column to be reduced. Vaporous piperazine was then drawn off continuously via a side draw above the 4th tray of the bubble-cap tray column, condensed and finished. The ratio between the bottom draw and the side draw amount was approx. 1:1. Piperazine was obtained with a purity of >99.9% by weight. The color number and the color number stability were distinctly improved in comparison to the experiment according to Example 1. Color numbers of 16 APHA immediately after finishing and 42 APHA after 3 months were measured.

Claims (1)

1. A process for continuously, distillatively removing piperazine from an ethylenediamine-piperazine mixture under pressure at elevated temperature, by discharging the ethylenediamine at the top and the piperazine at the bottom of a distillation column, which comprises subjecting the piperazine directly to a circulation conveying it through an evaporator unit operated at a temperature of from about 160° C. to about 170° C. and returning it into the distillation column, and, after a residence time of from 30 min to about 60 min in the circulation system, discharging it in vapor form from a side draw in the lower region of the distillation column.
US11/494,733 2005-08-13 2006-07-28 Process for distillatively removing piperazine from an ethylenediamine-piperazine mixture Active US7271292B2 (en)

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DE102005038376A DE102005038376A1 (en) 2005-08-13 2005-08-13 Process for the distillative removal of piperazine from an ethylenediamine-piperazine mixture
DE102005038376.9 2005-08-13

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EP (1) EP1752454B1 (en)
JP (1) JP5158668B2 (en)
CN (1) CN1911914B (en)
AT (1) ATE394382T1 (en)
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ES (1) ES2304765T3 (en)

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* Cited by examiner, † Cited by third party
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DE102004038107A1 (en) * 2004-08-05 2006-03-16 Basf Ag Process for improving the color stability of piperazine
DE102009000678B4 (en) * 2009-02-06 2013-11-14 Wacker Chemie Ag Process for recovering ethylenediamine from its hydrochloride
JP2013060517A (en) * 2011-09-13 2013-04-04 Tosoh Corp Heavy metal treating agent, manufacturing method of heavy metal treating agent, and method for treatment of heavy metal-containing material using the same
CN102977055B (en) * 2012-11-21 2015-10-28 西安近代化学研究所 A kind of separation method of piperazine

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3105019A (en) 1958-11-04 1963-09-24 Union Carbide Corp Recovery of piperazine
US3331756A (en) * 1964-11-23 1967-07-18 Jefferson Chem Co Inc Azeotropic distillation of diethylene-triamine and aminoethylethanolamine from piperazine residue
GB1263588A (en) 1969-10-28 1972-02-09 Bp Chem Int Ltd Purification of polyethylene polyamides
US20070043217A1 (en) * 2003-10-17 2007-02-22 Basf Aklengesellschaft Method for the distillative separation of mixtures containing ethyleneamines

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB816037A (en) * 1957-01-18 1959-07-08 Pfizer & Co C Process for preparation of piperazine
JPS51136183A (en) * 1975-05-20 1976-11-25 Hitachi Cable Ltd Insulated cable
JPH08134016A (en) * 1994-11-07 1996-05-28 Toagosei Co Ltd Purification of polymerizable liquid
CN1235892C (en) * 2000-08-25 2006-01-11 化学工业部西北化工研究院 Gas-solid catalytic process for synthesizing piperazine from ethanediamine and ethandiol
CN1634896A (en) * 2003-12-30 2005-07-06 天津大学 Method for continuous synthesis of piperazine series compounds in fixed bed

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3105019A (en) 1958-11-04 1963-09-24 Union Carbide Corp Recovery of piperazine
US3331756A (en) * 1964-11-23 1967-07-18 Jefferson Chem Co Inc Azeotropic distillation of diethylene-triamine and aminoethylethanolamine from piperazine residue
GB1263588A (en) 1969-10-28 1972-02-09 Bp Chem Int Ltd Purification of polyethylene polyamides
US20070043217A1 (en) * 2003-10-17 2007-02-22 Basf Aklengesellschaft Method for the distillative separation of mixtures containing ethyleneamines

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CN1911914A (en) 2007-02-14
DE502006000740D1 (en) 2008-06-19
DE102005038376A1 (en) 2007-02-15
US20070037980A1 (en) 2007-02-15
EP1752454A1 (en) 2007-02-14
JP5158668B2 (en) 2013-03-06
ES2304765T3 (en) 2008-10-16
EP1752454B1 (en) 2008-05-07
CN1911914B (en) 2010-10-13
JP2007051142A (en) 2007-03-01
ATE394382T1 (en) 2008-05-15

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